Production of benzanthrone vat dyes methylated in 9-position



Patented Apr. 3, 1951 PRODUCTION OF BENZANTIHRONEE v'A'r DYES METHYLATED 1 9-POSI'1ION David I. Randall, Plrillipsburg, N. J., assignor' to General Aniline & Film Corporation, New N. Y., a corporation of Delaware York, v

No Drawing; Application February 17, 1949,

p Serial No. 77,053 Y (01. 260-274) 2 Claims. 1

The present invention relates to vat dyes of the benzanthrone series having a methyl group unstable in sulfuric acid solution. In addition,

the intensities of its prints are Weak andthe shades thereofjare too -much'onthe greenish side.

\ It is proposed in U. S; P. 1,832,236 to obtain purer dyeings thancan-be obtained with Indanthrene Olive Green B by alkylating the nitrogen atom of the older dyestuff. It is indicated that the resulting product yields dyeingswhich are'blu'e-green incolor. These N-alkyl derivafrom the standpointfof the intensity and of the prints obtainedtherewith and the stability of the dyes to sulfuric acid.

Vat dyes ofz'the Indanthrene Olive Green B type containing a methyl group in the 9-position of the ben zan throne ring, the method of producing such'dye's, and the di-sulfuric acid esters of the dyes constitute the purposes and objects ofthe present invention) V [a The vat dyes contemplated hereinmay be pro-I duced in sevei'al ways; Onemethod involvesithe: condensation of 9-chloromethyl 4-bromobenzanthrone' with a' I aminoanthraquinone iOLilowed by caustic fusion tothe final dye. Rather peculiarly, under the conditions of the reaction, only the bromine atom" in 4-position of the benzanth-rone reacts with the aminoanthra tives'are even poorer printers than the older'dye;

Furthermore, prints produced from the N-alliyl derivative, like those of the Indanthrene-Olive Green'B, are of poor intensity and do not have satisfactory' fastness properties;

It has now been discovered that benzanthrone dyes of the Indanthrene Olive GreenB typecontaining a methyl group in the'Q-positiOn ofthe benzanthronering are capableof' printing in full olive shades of good strength-"and excellent fastnessproperties The new products, despite the fact that they are isomers of thecompounds de scribed in U. S. P. 1,832,236, are far superior lAniline 'qninonei the chlorine atom in theQ-rn'ethyI group being split ofi as hydrochloric acid. 1

Another method for producing the vat dyes involves the condensation of any primary aromatic amine, such as aniline, toluidine, l-aminonaphthalene, z-aminonapht'halene, and the like with 4-bromo-9-chloromethylbenzanthrone at a temperature below which the bromine in 4-position does not react, i. e.,-be1ow C. A 1- aminoanthraquinone isthen reacted with the bromine in 4-.position and the intermediate thus obtained ring closedrby fusion in caustic alkali. During fusion the arylamino moiety is removed by reductive-c1eavage.

The production of the vat dyes as above may be graphically illustrated as follows:

"on" on shades The dyes may also be obtained by condensing a l-amino-anthraquinone with a quaternary ammonium salt of 4-bromo-9-chloromethyl benzanthrone followed by caustic fusion. The quaternary ammonium salt may be of any tertiary amine such as pyridine, dimethyl aniline, diethyl H CHr-N l-amino anthroquione densing the 4-bromo-9-chloromethyl benzan- 1 throne with a l-amino-anthraquinone.

aniline, quinoline, morpholine, trimethylamine,

triethylamine, tributylamine, and the like. The structure of thequaternary ammonium salt, assuming pyridine to be the tertiary amine, is as follows:

The intermediate subjected to ring closure in method (1) above is prepared by heating to .methyl benzanthrone is condensed with the priimary aromatic amine such as aniline by heating the reactants to a temperature of about 100 to 120 C. for several hours. The 4-bromo-9-phenylaminobenzanthrone is isolated by adding an excess of aqueous hydrochloric acid and filtering. The-arylamino benzanthrone is then condensed with a l-amino-anthraquinone by heating in a reaction mixture of the type employed for con- The quaternary ammonium compound employed in the third method may be prepared by heating 4-bromo-9-chloromethyl benzanthrone with the desired tertiary amine such as pyridine to a temperature ranging from about 80-125 C. Such quaternary ammonium compound is then condensed with the l-amino-anthraquinone in the manner outlined above.

Ring closure of the various intermediate con- I densation products to the desired vat dye may be effected in a melt of potassium hydroxide containing an alcohol such as methanol or ethanol and maintained at a temperature of from 110- 150 C.

The 4 bromo 9 chloromethyl benzanthrone may be obtained by heating 4-bromo benzanthrone dissolved in 96% sulfuric acid with dichlor-dimethyl ether while adding the latter dropwise to the sulfuric acid solution of the 4- bromo benzanthrone. The temperature after the addition is increased to 60 C. and held for 16 hours. A violet-red solution results and this is poured into ice and water from which a bright yellow solid precipitates. The solid is removed by filtration, washed free of acid, and dried.

Suitable 1-aminoanthraquinones which may be utilized for forming the vat dyes hereof are those of the following formula:

wherein one X is hydrogen, amino, benzoylamino, acetylamino or alkoxy, i. e., methoxy, ethoxy, butyroxy, propoxy, or the like, and the other K5 are hydrogen. Examples of such compounds are: l-amino-anthraquinone, 1.4-diamino-anthraquinone, 1.8-diamino-anthraquinone, 1.5 diaminoanthraquinone, none, 1 amino 4 ethoxy anthraquinone, 1-amino-5-methoxy-anthraquinone, 1-amino-8- methoxy-anthraquinone, 1 amino 4 benzoylamino-anthraquinone, 1-amino-5-benzoylaminoanthraquinone, 1-amino-4-acetylamino-anthral-amino-4-methoxy-anthraqui- .duinon 1ramiuo-5acetylamino anthraquinone.

' wherein X has thevalues'given above.

Such compounds may be converted. into their di-sulfuric acid esters by conventional procedure, 1. e., by heating the vat dye in an anhydrous medium comprising pyridine, an addition product of pyridine and sulfur Ztrioxide iron and cuprous chloride.

The dyeings obtained irom the leuco sulfuric acid esters of the involved vat dyes are of a dif- .ferent shade .from that obtained from the vats themselves, being shifted .incolor to "a greenish.- gray shade. It is recognized in the art that; the dyeings ,obtained' from .leuco esters of vat dyes where thedyeings are of ashade difierent from that obtained from the vat dye proper are almost always of very poor fastness properties. Very peculiarly, however, thedyeings obtained 'with the-.leuco esters of the presentv vat dyeshaveexcellent .fastness ..properties,. being .equal in. this .respect to the olive dyeir gs obtained from the wt dyes per ,se.

The inventionis further illustrated bythe fol- .lowing exampleabutit is to be understood that the invention is not restricted thereto.

Example I A mixture of 30.0 gramsof bbromo-Q-chloromethylbenzanthrone, 1'7 .5 grams" of 1,-aminoanthraqu'inone, 15.9 grams of anhydrous sodium carbonate, 1 gram of copper acetateffi grams of sodium acetate, and 210 cc. of nitrobenzene are stirred and heated at 205 C. for 4 hours. Nitro- -benzene is removed by steam. distillation and the violet precipitate isfilteredofi and dried-(weight 39.3 grams) 'For preparation of the olive. dyestuffi, a melt is jprepared from 150 grams of potassium hydroxide and 200 cc. of ethanol. To this, is. addedZ-l grams of the finely divided condensation product from above. Atemperature of 119-125 C.-is maintained for 3.5 hours. The black melt is poured excepting that the l-amino-anthraquinone is re.-

assign;

A- suspension of 34-grams oi the phenyla minp condensation product, 18 grams.. of; l-am-inoanthraquinone, 5 grams of anhydrous-sodium acetate, 10 grams of calcined soda ash, Lgram of copper acetate and-200 cc. of nitrobenzene are heated at 205 C. for 4 hours. After steam distillation and filtration, 42.2 grams of dye intermediate were obtained. (Nitrogen calc. 5.0%;

found LQ.)

Ring closure to the dye was performed as in Example I. From 40 grams of starting material 31.5 gramsof dye were. obtained. The, loss in weight corresponds almost exactly to cleavage of the aniline moiety. (Nitrogen calc. 3.1%, found 3.2%).

Example 'III A solution of 35.8 grams of 4.-bromo-.9,-chloromethylbenzanthrone, 34.2 grams of l-amino-5 benzoylaminoanthroquinone, 20 grams of calcined soda ash, 15 grams. of sodium acetate, 3 grams of copper acetate, and 400 cc. of nitrobenzene are heated for 4.5 hours at- 205? C; The condensation product is isolated :as :in Example I. The yield amounts to 55.5-grams.

For ringclosure, a melt ismade up from 400 grams of potassium hydroxide and 400 cc. of methanol. To this is added52 grams of the intermediate condensation product from above. A temperature of -142 C. is held for-2 hours and the dye is worked up as-in Example I.

From this procedurewas obtained:37.5 grams of debenzoylated dyestufi. Benzoylation with benzoyl chloride in nitrobenzene by known meth ods yields a dyestuif which-gave a bright yellowish olive shade yielding oncotton considerably yellower and brighter shades'than the dye of Example Iand possessing good =fastness properties.

Example IV The procedure is the same as in Examplelll excepting that the 'l-amino-fi-benzoylaminoanthraquinone is replaced by 1.5- diamino-anthraquinone. The dyestufi obtained upon benzoylation is the same as that of Example III.

Example V The procedureisthesame asin Example I placed by 1amino--methoxy anthraquinone.

The resulting dye yieldsgrayershades than the dyes of Example I..

Example VI The procedure is the same as. in Example II excepting that the i-bromo-9-phenylamino methyl benzanthrone is replaced byan' equivalent amount of the quaternary ammonium salt of flask was replaced by carbon dioxide.

pyridine with 4-bromo-9-ch1oromethylbenzanthrone. The dyestuff is the same as that of Example II. I 7

The quaternary ammonium salt is prepared as follows: 20 grams of crude 9-chloromethyl-4- bromobenzanthrone and 250 cc. of pyridine are heated on a steam bath at 95 C. for 1.5 hours while stirring. The yellow compound which precipitates is filtered, washed with acetone and dried. The product is soluble in water with a slight greenish fluorescence and is decomposed readily by warming with an aqueous base.

Example VII The procedure is the same as in Example II excepting that the -bromo- -phenylamino methyl-benzanthrone is replaced by an equivalent quantity of the quaternary ammonium salt obtained as above but while using trimethylamine as the tertiary amine in place of pyridine. The

dyestufi is the same as that of Example II.

The same dye is obtained when using the quaternary ammonium salt from dimethyl aniline and 4-bromo-9-chloromethyl benzanthrone.

EzrampZe VIII The procedure is the same as in Example I excepting that the l-amino-anthraquinone is replaced by 1amino-5-ethoxy-anthraquinone. The dye is similar to that of' Example I.

V Example IX 7 The procedure is the same as in Example I excepting that the"1-amino-anthraquinone is replaced by 1.8-.diarnino anthraquinone. Upon b enzoylation as in Example III, a product is obtained which yields dyeings similar to those of Example III.

Example X A 500 cc. S-necked flask equipped with-an agitator, thermometer and reflux condenser was charged with 200 cc. of pyridine, dry. The pyridine was colled-to C. and while still cool- "ing, cc. of chlorosulfonic acid was dropped in over a period of 10 minutes. The temperature roseto about 32 C. Crystals of the pyridine and chlorosulfonic acid addition compound separated at this temperature. In-order to have a clear solution the temperature was raisedto 50 C. At'48- C. 22.5 grams of the product of Example I, '7 grams of iron by hydrogen and .2 gram of cuprous chloride were charged within 6 minutes. During the charging operation the temperature had droppedto 43 C. The air in the reaction While stirring without bath, the temperature went down to 35 C. within 30- minutes.- With the aid of a warm water bath of 47 C., the temperature was raised to 46 C. in 8 minutes. The charge was agitated at 46-48 C. for 2 hours. Then legrams of iron by hydrogen were'charged and efficient agitation wascontinued at 46-48 C. for 2 hours more. The reaction product was poured slowly into a solution of 64 gramsof soda ash in 375 cc. of Water in a 3-liter S-necked flask.

Rinsing water", wa s used to get an the material out of the reaction vessel. Finally enough water was added to'bring thetotal volume up to 1200' 'cc. The 3-necked flask was equipped with a thermometer, a capillary tube and an Eastman condenser in connection'with an ordinary con- ...denser.,.,, A distillation under diminished pressure, was performed using an aspirator and a ..steam bath. 343, grams of pyridine and water -distilled over in this case at 24 C. under 30 mm. x

pressure during 45 minutes. Since .a distinct pyridine odor was observed, 300 cc. offwater was added. The vacuum distillation. was continued until the pyridine odor had "practically disappeared.- The content of the flask was filtered and washed with hot water in small amounts until the filtrate was colorless, indicating that all the di-ester was washed out. The remaining irori sludges on the filter were dried. Weight=16.1

gram. I

The combined di-sulfuric vester solution and washings had a volume of 1500 cc. In'order to have enough alkalinity, 10 cc. of 20% sodium hydroxide solution was added. The di-ester was salted out with sodium chloride at the rate of 25 grams per cc. of solution. In this case 3'75 rams of sodium chloride, were used. The salt was added at 25 C. during 10 minutes. After all\ the salt had been introduced, the mixture was stirred for 1 hour and then allowed to stand overnight in a dark place without agitation. The filtration was done at 20 C. The di-ester cake was washed with a small amount of washing solution made up of 100 parts of water, 20 parts of sodium chloride and 0.5 part of sodium hydroxide. Finally the cake was sucked down sharply onthe Buechner funnel and dried in a vacuum desiccator over calcium chloride.

The dyeings obtained with the disulfuric acid, ester are a grayish-green in color, having excellent fastness to washing and light.

I claim: I

1. The process of producing vat dyes of the benzanthrone series containing a methyl group in 9-position of the benzanthrone ring which comprises heating in the presence of. an alkali .a l-amino-anthraquinone of the following formula:

III NH:

wherein one X is selected from-the class consist ing of hydrogen, amino, benzoylamino, acetylamino and alkoxy, and the other X s are-hydrogen, with a 4 bromo 9 chloromthyl benzanthrone. and subjecting the resultingcondensation' product to alkali fusion to efiectrih'g closure thereof.

2. The process of producing a vat dye of the benzanthrone series containing a methyl group in the 9-position thereof which comprises heating in the presence of an alkali l-aminoanthraquinone with i bromo 9 chloromethyl benzanthrone and subjecting the resulting condensation productto an alkali fusion to effect ring closure thereof.

' DAVID I. RANDALL.

REFERENCES CITED 7 The following references are of record in th file Of this patent 5 v UNITED STATES PATEN 3 

1. THE PROCESS OF PRODUCING VAT DYES OF THE BENZANTHRONE SERIES CONTAINING A METHYL GROUP IN 9-POSITION OF THE BENZANTHRONE RING WITH COMPRISES HEATING IN THE PRESENCE OF AN ALKALI A 1-AMINO-ANTHRAQUINONE OF THE FOLLOWING FORMULA: 